KR100662160B1 - Process film for use in producing ceramic green sheet and method for producing the film - Google Patents

Abstract

The process film for producing a ceramic green sheet of the present invention is a process film comprising a base film and a cured layer of a silicone resin composition provided thereon, wherein the cured layer is a light having a coating amount of 0.01 to 0.2 g / m ² expressed in solid content. The sensitizer-containing addition reaction type silicone resin composition layer is formed by heat treatment at a temperature in the range of 40-120 ° C., followed by ultraviolet irradiation. This process film is excellent in the coating property of a ceramic slurry and the peelability of a ceramic green sheet, and has the high flatness which is not conventional.

Description

PROCESS FILM FOR USE IN PRODUCING CERAMIC GREEN SHEET AND METHOD FOR PRODUCING THE FILM}

The present invention relates to a process film for producing a ceramic green sheet and a method of manufacturing the same. More specifically, it is used in producing ceramic green sheets used for ceramic capacitors (capacitors), stacked inductor elements, and the like; A cured layer of a silicone resin composition having preferred adhesion to a base film; Since both the coating property of a ceramic slurry and the peelability of a ceramic green sheet are excellent, it is related with the process film which has high flatness which cannot be realized conventionally, and the method of manufacturing this efficiently.

In recent years, in response to the trend of miniaturization and weight reduction of electronic devices, thinning and lightening of electronic device components themselves are required.

For example, an electronic component such as a capacitor having a lead and a multilayer inductor element simultaneously fires a laminate of a ceramic layer and a conductive layer having a predetermined pattern shape to form a monolithic structure in which an internal conductor is mounted. Although the technology can be miniaturized by practical use, miniaturization is still required.
In general, the ceramic capacitor is prepared by first mixing a binder or an organic solvent with a high dielectric constant ceramic powder such as a compound having a perovskite crystal structure such as barium titanate to prepare a slurry; Coating a process film, such as a polyethylene terephthalate film, with the resulting slurry; Drying the coating to prepare a ceramic green sheet; An electrode pattern is then formed on the ceramic green sheet by screen printing or the like using a conductive paste; Then peeling off the ceramic green sheet from the process film; Stacking a plurality of printed ceramic green sheets in a predetermined order; Compressing the laminate under heating; It is cut into a predetermined chip shape; And sintering the chips by firing.

On the other hand, multilayer inductor elements usually use a ceramic ceramic powder such as ferrite to produce a ceramic green sheet on a process film in the same manner as described above; Forming a coil pattern on the ceramic green sheet by screen printing or the like using the conductive paste; Peeling off the ceramic green sheet from the process film; The stacked stacked inductor element is fabricated by the steps of chip-forming in the same manner as described above.

The chip-shaped ceramic capacitor and multilayer inductor element obtained are required to be further miniaturized in response to the miniaturization request as described above. In order to meet this demand, the thickness of the ceramic green sheet needs to be further reduced at present 5 to 20 mu m.

When the ceramic green sheet is thinned to this extent, the conventional process film cannot cope with the demand, and the high performance film, that is, the coating property of the ceramic slurry and the peelability of the ceramic green sheet are both excellent, and there is no heat shrinkage or wrinkle, and excellent high flatness. It is indispensable to realize a process film.

Conventionally, a polyethylene terephthalate film (PET film) subjected to a peeling treatment with a thermosetting addition reaction type silicone resin release agent has been generally used as a process film. However, in order to ensure a stable cured film, the thermosetting addition-reaction type silicone resin releasing agent must be crosslinked at a high temperature of typically 140 ° C. or higher, so that heat shrinkage of the PET film necessarily occurs in the delamination step. Heat shrinkage or wrinkles found in PET films lead to the problem of not being able to form uniform thin sheets when forming films from ceramic slurries.

In such a situation, there is an attempt to perform processing with a thermosetting addition reaction type silicone resin releasing agent by delaying the processing speed at low temperature (110 to 130 ° C.) so as to suppress heat shrinkage or wrinkles as much as possible. However, this not only lowers the productivity but also causes insufficient curing, causing problems such as adhesion stability of the silicone resin to the PET film, coating property of the ceramic slurry, and the like.

As a silicone resin releasing agent that can be cured at low temperatures, a single ultraviolet curing silicone resin releasing agent having functional groups such as epoxy group, acrylic group, and mercapto group is known, but such a releasing agent is difficult to obtain a uniform silicone resin coating surface, The problem is that the peelability is bad and the stability is weak.

In the above background, an object of the present invention is used in the manufacture of ceramic green sheets used in ceramic capacitors or stacked inductor elements; A cured layer of a silicone resin composition is provided that provides adequate adhesion to the base film; The coating property of the ceramic slurry and the peelability of the ceramic green sheet are excellent; It relates to providing a process film having high flatness not realized in conventional films, and also to a method for effectively producing the process film described above.

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As a result of intensive and extensive research accumulated in the present invention to develop a process film for producing a ceramic green sheet having excellent functionality as described above, as an addition reaction type silicone resin composition containing a photosensitizer as a release agent After coating the base film to a specific thickness, the resulting coating is heated at a predetermined temperature and cured by in-line ultraviolet irradiation, whereby a cured silicone resin composition layer having excellent adhesion to the base film is formed and the cured layer It has been found that the film to which the is attached is applied as a process film suitable for the purpose of the present invention. The present invention has been accomplished based on the above findings and information.

That is, the present invention;

(1) a process film comprising a base film and a cured layer of a photosensitizer-containing addition-reactive silicone resin composition provided thereon, wherein the cured layer is light in a coating amount of 0.01-0.2 g / m ² , indicated by a solid content. A process film for producing a ceramic green sheet, wherein the sensitizer-containing addition-reactive silicone composition layer is heat-treated at a temperature in the range of 40 to 120 ° C., followed by ultraviolet irradiation.

(2) the process film for producing a ceramic green sheet according to the above (1), wherein the base film is polyethylene terephthalate,

(3) The process film for producing a ceramic green sheet according to the above (1) and (2), wherein the addition reaction type silicone resin composition contains polydimethylsiloxane containing a vinyl group as a functional group,

(4) The process film for producing a ceramic green sheet according to the above (1) or (2), wherein the addition-reaction type silicone resin composition contains polydimethylsiloxane containing a hexenyl group as a functional group;

(5) The ceramic green according to (1) or (2), wherein the addition-reaction type silicone resin composition contains a mixture of polydimethylsiloxane having a hexenyl group as a functional group and polydimethylsiloxane having a vinyl group as a functional group. Process film for sheet manufacturing,

(6) providing a base sensitizer-containing reaction-reactive silicone resin composition layer having a coating amount of 0.01 to 0.2 g / m ² represented by a solid content, and heat-treated at a temperature in the range of 40 to 120 ° C., Moreover, the manufacturing method of the process film for ceramic green sheet manufacture characterized by irradiating and hardening an ultraviolet-ray to a silicone resin composition layer.
To provide.
Best mode for carrying out the invention

The process film (hereinafter simply referred to as "process film of the present invention") for producing the ceramic green sheet according to the present invention includes a base film and a cured layer of a silicone resin composition provided thereon. The base film is not particularly limited, but may be appropriately selected from films widely known to be used as base films for process films for producing ceramic green sheets. Examples of such films include polyester films such as polyethylene terephthalate and polyethylene naphthalate; Polyolefin films such as polypropylene and polymethylpentene; Polycarbonate film; Although a polyvinyl acetate film etc. are mentioned, Among these, a polyester film is preferable and a biaxially stretched polyethylene terephthalate film is especially suitable. As for a base film, what has a thickness of 12-125 micrometers is used normally.

The cured layer of the silicone resin composition to be provided on the base film in the process film according to the present invention is to cure the photo-sensitizer-containing addition reaction type silicone resin composition layer in combination with heat treatment and ultraviolet irradiation treatment.

The conventional thermosetting addition reaction type silicone resin releasing agent needs to be subjected to high temperature heat treatment in order to obtain a stable cured film. When low temperature heat treatment is applied, curing is insufficient and therefore it is difficult to obtain adequate performance. As an alternative, a method of increasing the amount of catalyst or decreasing the processing speed is proposed. However, an increase in the amount of catalyst affects the life of the vessel and a decrease in the processing speed lowers the productivity.

In contrast to the above, the present invention adds a photosensitizer to a conventional release agent, that is, a thermosetting addition reaction type silicone resin release agent, and uses a combination of thermosetting and ultraviolet curing, thereby providing a silicone resin composition having desirable adhesion to a base film. Forming a cured layer; High flatness regardless of heat shrink or wrinkle; The coating film and stability of a ceramic slurry are favorable, and the process film which has a ceramic green sheet peelability is provided.

The addition reaction type silicone resin composition containing the photosensitizer used in the present invention is a main component addition reaction type silicone resin (e.g., polydimethylsiloxane having a functional group) and a crosslinking agent (e.g., silicone resin such as polymethylhydrogensiloxane). Crosslinking agents); Catalysts (eg platinum catalysts); It is a composition containing a photosensitizer and, if necessary, an addition reaction inhibitor, a release control agent such as a silicone gum and a silicone varnish, and an adhesion improving agent.

The above-described addition reaction type silicone resin is not particularly limited, but may be selected from various resins, such as those conventionally used as a conventional thermosetting addition reaction type silicone resin releasing agent. Examples of the addition-reaction type silicone resin include at least one selected from polyorganosiloxanes having an alkenyl group as a functional group in a molecule thereof. Preferred examples of the polyorganosiloxane containing an alkenyl group as a functional group in the molecule include polydimethylsiloxane containing a vinyl group as a functional group, polydimethylsiloxane containing a hexenyl group as a functional group, and mixtures thereof. Particularly preferred among these is polydimethylsiloxane containing a hexenyl group as a functional group in terms of securing excellent curability and stable peelability of the green sheet.

Examples of crosslinkers include polyorganosiloxanes having at least two hydrogen atoms each bonded to one silicon atom in one molecule, in particular dimethylhydrogen-siloxy group terminal blockade dimethylsiloxane / methylhydrogen-siloxane copolymers, Trimethylsiloxy group terminal blockade dimethylsiloxane / methylhydrogen-siloxane copolymer, trimethylsiloxy group terminal blockade poly (methylhydrogen-siloxane), poly (hydrogen-silsesquioxane) and the like. The amount of the crosslinking agent exemplified is selected from the range of 0.1 to 100 parts by weight, preferably 0.3 to 50 parts by weight, based on 100 parts by weight of addition reaction silicone.

Examples of silicone resins having a function for modifying the peeling properties of the cured film include polyorganosiloxanes each containing no alkenyl group and hydrogen atom bonded to silicon atoms in one molecule, and in particular, trimethylsiloxy group end-blocked poly Dimethylsiloxane, dimethylphenylsiloxy group terminal blockade polydimethylsiloxane, and the like.

As catalysts, platinum-based compounds such as particulate platinum, particulate platinum adsorbed on a carbon powder carrier, chloroplatinic acid, alcohol-modified platinum chloride, chloroplatinic acid / olefin complexes, palladium catalysts and rhodium catalysts are used. The usage-amount of the said catalyst is the range of 1-1000 ppm with respect to the total amount of addition reaction type silicone resin and a crosslinking agent.

On the other hand, the photosensitizer used in the addition-reactive silicone composition is not particularly limited but is preferably used selectively from those conventionally used in ultraviolet curable resins. Examples are benzoin, benzophenone, acetophenone, α-hydroxy ketone, α-aminoketone, α-diketone, α-diketone dialkyl acetal, anthraquinone, thioxanthone and other compounds. .

Examples of benzoin include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, and benzoin socked end of polydimethylsiloxane by ether bonding. Compound bound to the compound. Examples of benzophenones are benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, trimethylsilylbenzophenone, 4-methoxybenzophenone and the like. Examples of acetophenones are acetophenone, dimethylaminoacetophenone, 3-methylacetophenone, 4-methylacetophenone, 4-allylacetophenone, 3-pentylacetophenone and propiophenone. Examples of α-hydroxy ketones include 2-hydroxy-1- (4-isopropyl) phenyl-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methylpropan-1-one and 1-hydroxycyclohexylphenylketone. Examples of α-aminoketones are 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholi Nophenyl) butan-1-one and the like. Examples of α-diketones are benzyl and diacetyl and the like. Examples of α-diketone dialkylacetals are benzyldimethyl acetal and benzyldiethyl acetal. Examples of anthraquinones are 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-tert-butyl anthraquinone, 2-amino anthraquinone and the like. Examples of thioxanthones are 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, and the like. Examples of other compounds include tertiary amines such as triphenylamine and p-dimethylamino benzoic acid esters, and also azo compounds such as azobis (isobutyronitrile).

The photosensitizer of the above-mentioned example can be used individually or in combination of 2 or more types. The amount used is selected from 0.01 to 30 parts by weight, preferably 0.05 to 20 parts by weight, based on 100 parts by weight of the total amount of the addition reaction type silicone resin and the crosslinking agent used as the main component.

The above-described addition reaction inhibitors are components used for the purpose of imparting storage stability at room temperature to the composition, particularly 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol, 3-methyl-3-pentene-1-yne, 3,5-dimethyl-3-hexene-1-yne, cyclic tetravinylsiloxane, benzotriazole, etc. are mentioned.

In the present invention, the coating liquid having a viscosity enough to enable the coating is prepared by adding a plurality of kinds of components used as necessary in a predetermined ratio in an addition-reactive silicone resin composition containing a photosensitizer in a suitable organic solvent. . The organic solvent is not particularly limited, but one suitable for use is selected from various solvents including, for example, hydrocarbons such as toluene, hexane and heptane, ethyl acetate, methyl ethyl ketone and mixtures thereof.

The coating solution prepared according to the present invention is applied to one or both sides of the base film according to methods such as gravure coating method, bar coating method, spray coating method, spin coating method and so on in terms of solid content of 0.01 to 0.2 An addition reaction type silicone resin composition layer containing a photosensitizer may be prepared in a coating amount in the range of g / m ² . When the coating amount is less than 0.01g / m ² , the peelability is not good, whereas when the coating amount is more than 0.2g / m ² , the coating property of the ceramic slurry is weakened, such as the occurrence of repulsion when coating the ceramic slurry. In consideration of the peelability of the ceramic green sheet, the coating property of the ceramic slurry, and the like, the coating amount is preferably in the range of 0.05 to 0.12 g / m ² , particularly preferably 0.07 to 0.1 g / m ² .
The base film provided with the addition reaction type silicone resin composition layer according to the present invention is first heat-treated at a temperature in the range of 40-120 ° C. to precure the resulting layer. If the heat treatment temperature is less than 40 ° C., there is a concern that the drying or precure may be insufficient, while if it is above 120 ° C., heat shrinkage or wrinkles may occur, and thus, the object of the present invention may not be achieved. In consideration of drying, precuring, heat shrinking or wrinkling and other variables, the heat treatment temperature is preferably in the range from 50 to 100 ° C.
The precured layer of the heat-treated addition reaction silicone resin composition is completely cured by performing in-line ultraviolet irradiation. Useful ultraviolet lamps may use known lamps such as high pressure mercury lamps, metal halide lamps, high power metal halide lamps, electrodeless ultraviolet lamps and the like. Among these, an electrodeless ultraviolet lamp is preferred from the viewpoint of low thermal damage to the base film and excellent curability of the silicone resin composition layer due to appropriate ultraviolet light emission efficiency, infrared irradiation amount and the like. The electrodeless ultraviolet lamp described above is commercially available from D Corporation, H Bulb, H + Bulb, V Bulb, etc., of Fusion Corporation, among which H Bulb and H + Bulb are particularly preferable. The ultraviolet irradiation power is appropriately selected and usually ranges from 30 W / cm to 600 W / cm, preferably 50 W / cm to 360 W / cm.

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Although the temperature at the time of ultraviolet irradiation process is not specifically limited, It is the temperature of the heating conditions or room temperature immediately after heat processing at the time of inline execution.

In the above-described manufacturing process, the cured layer of the addition-reaction type silicone resin composition is formed on one side or both sides of the base film with excellent adhesion, there is no heat shrinkage or wrinkles, extremely high flatness, and coating property of the ceramic slurry and It is possible to obtain the process film of the present invention with excellent peelability of the ceramic green sheet.

The process film according to the invention is used in the manufacture of ceramic green sheets and is very suitable for producing ceramic green sheets having a thickness of about 20 μm or less, more preferably 10 μm or less, particularly preferably 6 μm or less.

Examples of the ceramic green sheet applied to the process film according to the present invention include a ceramic green sheet having a high dielectric constant and used for a chip-shaped ceramic capacitor, and a magnetic green sheet used for a chip-shaped multilayer inductor element. In particular, the process film according to the present invention is suitable for application in the production of green sheets used in ceramic capacitors having a miniaturized chip size of 1005 shape for miniaturized portable devices.

Ceramics contained in a ceramic green sheet having a high dielectric constant and used in ceramic capacitors, including PbTiO ₃ , KNbO ₃ , Pb (Ni _1/3 Nb _2/3 ) O ₃ as well as barium titanate (BaTiO ₃ ), and Cd ₂ Nb ₂ O _7, PbNb there may be mentioned a compound having a perovskite-type crystal structure such as ₂ O ₆ and PbTa ₂ O _6.

On the other hand, the magnetic ceramic contained in the ceramic green sheet used in the laminated inductor element includes Zn ferrite, Ni ferrite, Mn ferrite, Mg ferrite, Ni-Zn ferrite, Mn-Zn ferrite, and Mg- Spinel type ferrites, such as Zn type ferrite, Ni-Cu-Zn type ferrite, and Mg-Mg-Zn type ferrite, or hexagonal ferrite etc. are mentioned.

The ceramic green sheet may be prepared by mixing a ceramic powder, a suitable solvent and a binder such as a polyvinyl alcohol binder, a carboxymethyl cellulose binder, a butyral binder or an acrylic binder to prepare a slurry, and using the doctor blade or the like to produce a slurry. It is produced by coating a process film according to the invention and further drying the coating to form a ceramic green sheet having a thickness of 20 μm or less, preferably 10 μm or less, particularly preferably 6 μm or less.

When the green sheet is used as a ceramic capacitor, it is formed using the above-described high dielectric constant ceramic powder, and a desired electrode pattern (internal electrode) is formed through screen printing using a conductive paste for printing containing a metal conductor on the resulting green sheet. Pattern). The ceramic green sheet is peeled off the process film and is usually laminated into a plurality of sheets of at least 100 sheets, pressed under heating and cut into chips of appropriate size. Subsequently, the chip is subjected to sintering by sintering, whereby a ceramic capacitor having an internal electrode mounted and having a chip-shaped monolith structure is obtained.

When the green sheet is used in the laminated inductor element, the ceramic green sheet having the appropriate coil pattern (inner conductor pattern) is produced in the same manner as described above using the magnetic ceramic powder described above. Thereafter, the above-described method is repeated to obtain a multilayer inductor device having a monolithic structure in the form of a chip on which an internal conductor is mounted.

In the following, the present invention is described in more detail with reference to comparative examples and examples, but the present invention is not limited thereto.

Various characteristics of each of the process films obtained through the examples and the comparative examples were evaluated according to the evaluation procedures as described below.

(1) curability

Curing property was evaluated according to the following criteria by observing the phenomenon of damage (smear) and peeling (love-off) of the film by rubbing the surface of the cured layer on the process film ten times with a finger.

◎: No damage or peeling is observed.

○: slight damage is observed (practically no problem)

ㅿ: some damage and peeling are observed (sometimes causing practical problems)

x: significant damage and flaking observed (practically causes problems)

xx: Significant peeling is observed and hardening is insufficient.

(2) non-performance of silicone resin

The PET film is laminated on the cured coating layer of the process film, a 1.97 N / mm load is applied to the laminate, the laminate is left for 24 hours, after which the PET film is peeled off from the laminate, and the laminate surface is felt tip The marker was used to paint, and the presence of the silicone resin was confirmed according to the resilience strength, and the non-compliance of the silicone resin was evaluated according to the following criteria.

◎ No transition observed.

○: slight transition observed (practically no problem)

ㅿ: some transition is observed (sometimes causing practical problems)

x: relatively large transition observed (practically causes problems)

xx: significantly larger transitions are observed

(3) flatness (heat shrinkage or wrinkles)

Wrinkles on the process film were visually observed, the cured coating layer was coated with a ceramic slurry with a thickness of 6 μm, and the uniform coating was inspected to evaluate flatness according to the following criteria.

◎: Excellent.

○: good (practically no problem)

ㅿ: rather poor (sometimes causing practical problems)

x: poor (causes practical problem)

xx: extremely poor

(4) Adhesiveness of the hardened coating layer (after 70 days)

The adhesiveness of the cured coating layer was evaluated against the following criteria according to the method of observing peeling of the cured coating layer from the PET film after rubbing the surface of the cured coating layer on the process film ten times with a finger after 70 days of silicone treatment.

(Double-circle): Peeling was not observed at all.

○: slight peeling observed (practically no problem)

ㅿ: peeling is observed somewhat (sometimes causing practical problems)

x: A significant amount of peeling is observed (causes practical problems)

xx: Significant peeling is observed.

(5) Coating property of BaTiO ₃ slurry and coating property of ferrite slurry

Using a ball mill, 100 parts by weight of barium titanate (BaTiO ₃ ) powder or Ni-Cu-Zn-based ferrite powder, 10 parts by weight of polyvinyl butyral and 10 parts by weight of dibutyl phthalate are mixed with a mixed solution of toluene and ethanol, Dispersion produced a BaTiO ₃ slurry and a ferrite slurry, respectively. Each slurry was uniformly coated on the process film to maintain a coating thickness of 6 μm, and then dried to prepare respective green sheets. At this time, the coating property of the BaTiO ₃ slurry and the coating property of the ferrite slurry were evaluated according to the following criteria by visually observing the wettability (repulsion and nonuniformity of the coating) during slurry coating.

◎: Excellent.

○: good (practically no problem)

ㅿ: rather poor (sometimes causing practical problems)

x: poor (causes practical problem)

xx: extremely poor

(6) Peelability of BaTiO ₃ Green Sheet and Peelability of Ferrite Green Sheet

Each green sheet was made in the same manner as in (5) above, and the adhesive tape (produced under the trade name " 31B tape " of Nito Denko Corporation) was laminated. Each resulting sample was left for 24 hours at 23 ° C. and 65% R.H. and cut 20 mm wide. Using a tensile test apparatus, the process film of each sample was peeled off from the laminate at a 180 degree angle at a speed of 100 m / min, and the force (peel force) required for peeling was measured. In addition, the peelability from the peeling film was evaluated according to the following criteria using the green sheet produced by the coating machine.

◎: Excellent.

○: good (practically no problem)

ㅿ: rather poor (sometimes causing practical problems)

x: poor (causes practical problem)

xx: extremely poor

Example 1

Addition-reactive silicone resin release agent mainly composed of polydimethylsiloxane having a hexenyl group as a functional group and a crosslinking agent (polymethylhydrogen siloxane) (produced under the trade name "LTC-760A" by Toray, Dow Corning, and Silicon Corporation). To 100 parts by weight of 2 parts by weight of a platinum-based catalyst (produced under the trade name " SRX-212 " by Toray, Dow Corning, and Silicon Corporation) was added to prepare an addition reaction type silicone resin composition. 1 part by weight of acetophenone as a photosensitizer was added per 100 parts by weight of the main material described above. The mixture prepared in this manner was diluted with an organic solvent containing toluene as a main component to prepare a coating liquid having a concentration of 1% by weight solids.

The coating solution was uniformly coated with a thickness of 0.1 μm (coating amount of 0.1 g / m ² based on solid content) after drying on a 38 μm thick biaxially stretched PET film through a gravure coating method. The coated PET film was then heated in a hot air circulation dryer at 50 ° C. for 20 seconds and immediately afterwards using a conveyor UV irradiator equipped with a Fusion H bulb 240 W / cm (the hot cut filter uses a high diffusion type). Ultraviolet irradiation was carried out under the condition of a conveyor speed of 40 m / min. In this manner, the silicone resin composition was cured to prepare a process film.
Various features of the production process film are shown in Table 1.

Example 2

The process film was manufactured by repeating the method of Example 1 except that the temperature of the hot air circulation dryer was set to 90 ° C. instead of 50 ° C.
The performance of the obtained process film was the same as in the case of Example 1. Various features of the resulting film are listed in Table 1.

Example 3

Addition-reactive silicone resin release agent mainly composed of polydimethylsiloxane having a vinyl group as a functional group and a crosslinking agent (polymethylhydrogen siloxane) (produced under the trade name "SRX-211" by Toray, Dow Corning, and Silicon Corporation) 100 2 parts by weight of a platinum-based catalyst (produced under the trade name " SRX-212 " by Toray, Dow Corning, Silicon Corporation) was added to parts by weight to prepare an addition reaction type silicone resin composition. 1 part by weight of acetophenone, a photosensitizer, was added per 100 parts by weight of the main material described above. The mixture prepared in this manner was diluted with an organic solvent containing toluene as a main component to prepare a coating liquid having a concentration of 1% by weight solids. Thereafter, a process film was prepared in the same manner as in Example 2 using this coating solution.
Various features of the resulting film are shown in Table 1.

Example 4

An addition-reactive silicone resin composition containing polydimethylsiloxane containing a vinyl group as a functional group used in Example 3 and an addition-reactive silicone resin composition containing a polydimethylsiloxane containing a hexenyl group as a functional group used in Example 1 To prepare a mixture by mixing in a weight ratio of 1: 1. 1 weight part of acetophenone which is a photosensitizer per 100 weight ratio of main materials mentioned above was added. The mixture prepared in this manner was diluted with an organic solvent containing toluene as a main component to prepare a coating liquid having a solid content concentration of 1% by weight. Thereafter, a process film was prepared in the same manner as in Example 2 using this coating solution.
Various features of the resulting film are as shown in Table 1.

Comparative Example 1                 

The addition reaction type silicone resin composition used in Example 3 was diluted with an organic solvent containing toluene as a main component to prepare a coating liquid having a concentration of 1% by weight solids. The coating solution was applied to a biaxially stretched PET film in the same manner as in Example 1 and heat-treated at 110 ° C. for 30 seconds in a hot air circulation dryer to prepare a process film.
Various properties of the resulting film are as shown in Table 1.

Comparative Example 2

The process film was manufactured by repeating the method of Comparative Example 1 except that the temperature of the hot air circulation dryer was set to 150 ° C. instead of 110 ° C.
The various properties of the resulting film are listed in Table 1.

Comparative Example 3

A conventional ultraviolet curable epoxy ring-opening polymerization silicone resin releasing agent (produced under the "UV 9300" brand name from Toshiba Silicone Co. Ltd.) as a main component of polydimethylsiloxane containing an epoxy group was applied to a biaxially stretched PET film. Thereafter, the PET film coated without heat treatment was subjected to ultraviolet irradiation under the same conditions as in Example 1 to cure the silicone resin release agent to prepare a process film. The various properties of the resulting film are listed in Table 1.

Table 1-1

Curable Silicone Resin Non-Performing Flatness (heat shrinkage or wrinkles) Adhesiveness of the cured coating layer (after 70 days) Example 1 ◎ ◎ ◎ ◎ Example 2 ◎ ◎ ◎ ◎ Example 3 ◎ ◎ ◎ ◎ Example 4 ◎ ◎ ◎ ◎ Comparative Example 1 △ x △ x Comparative Example 2 ◎ ◎ xx ◎ Comparative Example 3 ◎ ○ ◎ ○

TABLE 1-2

Slurry coating Green Sheet Peelability BaTiO ₃ ferrite BaTiO ₃ ferrite Peel force (mN / 20mm) Peelability Peel force (mN / 20mm) Peelability Example 1 ◎ ◎ 5.39 ◎ 5.49 ◎ Example 2 ◎ ◎ 5.39 ◎ 5.49 ◎ Example 3 ◎ ◎ 9.41 ○ 9.51 ○ Example 4 ◎ ◎ 5.49 ◎ 5.59 ◎ Comparative Example 1 x x 16.66 xx 16.86 xx Comparative Example 2 xx xx - - - - Comparative Example 3 x x - x - x

Example 5

The coating amount based on solids instead of 0.1g / m ^2, except that it contained 0.04g / m ² was prepared to process the film by repeating the procedure of Example 2. The results are shown in Table 2.

Example 6

The coating amount based on solids instead of 0.1g / m ^2, except that it contained 0.06g / m ² was prepared to process the film by repeating the procedure of Example 2. The results are shown in Table 2.

Example 7

The coating amount based on solids instead of 0.1g / m ^2, except that it contained 0.12g / m ² was prepared to process the film by repeating the procedure of Example 2. The results are shown in Table 2.

Example 8

The coating amount based on solids instead of 0.1g / m ^2, except that it contained 0.20g / m ² was prepared to process the film by repeating the procedure of Example 2. The results are shown in Table 2.

TABLE 2

Slurry coating Green Sheet Peelability BaTiO ₃ ferrite BaTiO ₃ ferrite Peel force (mN / 20mm) Peelability Peel force (mN / 20mm) Peelability Example 5 ◎ ◎ 7.84 ○ 8.04 ○ Example 6 ◎ ◎ 5.39 ◎ 5.49 ◎ Example 7 ◎ ◎ 5.39 ◎ 5.49 ◎ Example 8 ○ ○ 5.59 ◎ 5.78 ◎

Example 9

The process film was manufactured by repeating the method of Example 3 except that the temperature of the hot air circulation dryer was set to 50 ° C. instead of 90 ° C. The results are shown in Table 3.

Example 10

The process film was manufactured by repeating the method of Example 3 except that the temperature of the hot air circulation dryer was set to 100 ° C. instead of 90 ° C. The results are shown in Table 3.

Example 11

The process film was manufactured by repeating the method of Example 3 except for setting the temperature of the hot air circulation dryer to 120 ° C. instead of 90 ° C. The results are shown in Table 3.

TABLE 3

Curable Flatness (heat shrinkage or wrinkles) Example 9 ◎ ◎ Example 10 ◎ ◎ Example 11 ◎ ○

In summary, the effects of the present invention are used when producing a ceramic green sheet used in ceramic capacitors, laminated inductor elements, and the like by providing a cured layer of a silicone resin composition by using heat treatment and ultraviolet irradiation treatment together on a base film; The cured layer of the silicone resin composition which has preferable adhesiveness with a base film is formed; The coating property of the ceramic slurry and the peelability of the ceramic green sheet are excellent; Moreover, the process film for ceramic green sheet manufacture which has high flatness which cannot be realized with the conventional film can be obtained easily.

Claims (6)

A process film comprising a base film and a cured layer of a photosensitizer-containing addition-reactive silicone resin composition provided thereon, wherein the cured layer includes a photosensitizer-containing addition in a coating amount of 0.01 to 0.2 g / m ² expressed in solid content. A process film for producing a ceramic green sheet, wherein the reactive silicone resin composition layer is formed by heat treatment at a temperature of 40-120 ° C. and ultraviolet irradiation treatment. The method of claim 1, The base film is polyethylene terephthalate, The process film for ceramic green sheet manufacture characterized by the above-mentioned. The method of claim 1, The addition reaction type silicone resin composition comprises a polydimethylsiloxane having a vinyl group as a functional group, the process film for producing a ceramic green sheet. The method of claim 1, The addition reaction type silicone composition comprises a polydimethylsiloxane having a hexenyl group as a functional group. The method of claim 1, The addition reaction type silicone resin composition comprises a mixture of polydimethylsiloxane having a hexenyl group as a functional group and polydimethylsiloxane having a vinyl group as a functional group. After preparing a photo-sensitizer-containing addition reaction type silicone resin composition layer having a coating amount of 0.01 to 0.2 g / m ² expressed in solid content on the base film, and then heat-treated at a temperature of 40-120 ° C., and then the silicone resin composition layer Irradiating and hardening to ultraviolet-ray, The manufacturing method of the process film for ceramic green sheet manufacture characterized by the above-mentioned.